Triarylmethane pigment, coloring composition containing same, colorant for color filter, and color filter

Abstract

The purpose of the present invention is to provide a triarylmethane pigment having excellent heat resistance and to provide a colorant for a color filter having good color characteristics by using a coloring composition using the triarylmethane pigment because the heat resistance of a conventional triarylmethane pigment is not sufficient. Provided are a triarylmethane dye represented by general formula (1), a coloring composition containing the dye, a colorant for a color filter, and a color filter. In # imgabs0 # formula (1), R1-R5 represent H, an alkyl group, an aromatic hydrocarbon group, or a heterocyclic group, R6-R10 represent H, a halogen atom, OH, CF3, NO2, CN, an alkyl group, or an alkoxy group, R11-R14 represent H, an alkyl group, or an aromatic hydrocarbon group, and at least one of R8 and R12-R14 represents an alkyl group or an aromatic hydrocarbon group. An represents an anion, and m represents a natural number.

Description

Technical Field

[0001] The present invention relates to a triarylmethane dye, a coloring composition containing the dye, a colorant for a color filter containing the dye or the coloring composition, and a color filter using the colorant. Background Art

[0002] Color filters are used in liquid crystal display devices, organic electroluminescent (organic EL) display devices, and solid-state imaging elements such as CCD and CMOS sensors, and have red pixels (R), green pixels (G), and blue pixels (B). The colorants used in color filters include pigments, dyes, etc., but when manufacturing color filters, they are exposed to high temperatures of more than 200°C, ultraviolet radiation, and other conditions, so pigments with better heat resistance and light resistance than dyes are usually used. For example, as a blue pigment for forming a blue pixel portion, ε-type copper phthalocyanine pigment (CI Pigment Blue 15:6) is usually used, and a small amount of purple dioxazine violet pigment (CI Pigment Violet 23) is added thereto for color adjustment as needed.

[0003] As a trend in recent years, image display devices are required to save power. In order to improve the utilization efficiency of backlight sources, the demand for high brightness of color filters is becoming increasingly high. In particular, for the blue pixel unit, the utilization efficiency of the backlight source is lower than that of the red pixel unit and the green pixel unit, and it is expected to be improved.

[0004] Pigments are generally insoluble in solvents and therefore exist in the form of fine particles in color filters made of resins, etc. Therefore, it is known that, for color filters using pigments, the reflection and scattering of transmitted light on the surface of pigment particles affects the reduction of brightness and color purity, and the depolarization effect caused by reflection reduces the contrast of color display devices.

[0005] In order to improve the problem of reduced brightness and reduced contrast, as a colorant, not only the previous pigments have been studied, but also the use of dyes (such as patent document 1) has been studied. Since the dye is soluble in a solvent, the color filter using the dye is suppressed in the depolarization effect compared with the case where only the pigment is used as a colorant, and the spectral characteristics are excellent, and the improvement of brightness, contrast, etc. is expected. Therefore, especially for the color filter of the blue pixel portion, the use of a dye with excellent solubility than the pigment is usually concerned.

[0006] Particularly, for triarylmethane pigments, since the spectral characteristics are good, examples (e.g., Patent Documents 2 and 3) of using them as colorants for color filters are proposed. However, when the triarylmethane pigments known to date are used for preparing color filters, there is a problem that the color tone is easily changed due to the thermal history in its manufacturing process, etc. In addition, Patent Document 4 discloses that the triarylmethane pigments with a specific structure show high stability under alkaline conditions, but there is no record about heat resistance.

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 06-075375

[0008] Patent Document 2: Japanese Patent Application Publication No. 2011-186043

[0009] Patent Document 3: Japanese Patent Application Publication No. 2012-083652

[0010] Patent Document 4: U.S. Patent Application Publication No. 2008 / 0108817

[0011] Non-patent document 1: Hiroshi Horiguchi, "A Review of Synthetic Dyes", Sankyo Publishing Co., Ltd., July 15, 1969, p.79-109 Summary of the invention

[0012] Heat resistance is an important property required in the manufacturing process of color filters. The present invention aims to provide a triarylmethane colorant having excellent heat resistance and to provide a colorant for a color filter having good color characteristics (color gamut, brightness, contrast, etc.) by using a coloring composition of the colorant.

[0013] The present inventors have conducted intensive studies to solve the above problems and have found a triarylmethane dye having superior heat resistance to conventional triarylmethane dyes.

[0014] 1. A triarylmethane coloring matter represented by the following general formula (1).

[0015]

Chemical formula 1

[0016]

[0017] [In formula (1), R 1 ~R 5 Each independently represents -H, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent,

[0018] R 1 With R 2, R 3 With R 4 They can bond to each other to form a ring.

[0019] R 6 ~R 10 Each independently represents -H, a halogen atom, -OH, -CF3, -NO2, -CN, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms which may have a substituent,

[0020] R 11 ~R 14 Each independently represents -H, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,

[0021] R 8 and R 12 ~R 14 At least one of them represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0022] An represents an anion, and m represents a natural number.]

[0023] 2. The triarylmethane dye according to 1., wherein in the general formula (1), R 1 and R 3 Each independently is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0024] 3. The triarylmethane dye according to 2., wherein in the general formula (1), R 1 and R 3 same.

[0025] 4. The triarylmethane dye according to 1., wherein in the general formula (1), R 5 It is a linear alkyl group having 1 to 3 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0026] 5. The triarylmethane dye according to 1., wherein in the general formula (1), R 11 For -H, R 8 , R 12 ~R 14 It is a linear alkyl group having 1 to 3 carbon atoms which may have a substituent.

[0027] 6. The triarylmethane dye according to 1., wherein in the general formula (1), An is a perfluoroalkylsulfonic acid anion, a perfluoroalkylsulfonylimide anion, a tris(trifluoromethanesulfonyl)methide anion or a heteropolyacid anion.

[0028] 7. The triarylmethane dye according to 1., wherein the triarylmethane dye of the general formula (1) has an absorption band with a maximum absorption wavelength of 570 nm to 640 nm in an ultraviolet-visible absorption spectrum (wavelength range of 350 nm to 800 nm) measured at 23° C. to 27° C. using a propylene glycol monomethyl ether (PGME) solution.

[0029] 8. The triarylmethane dye according to 1., wherein the 5% mass reduction temperature of the triarylmethane dye of the general formula (1) measured by TG-DTA (sample mass: 5.0 to 6.0 mg, heating rate: 10°C / min) using a thermogravimetric-differential thermal analyzer under a nitrogen gas flow (nitrogen flow rate: 50 mL / min) is 270°C or higher.

[0030] 9. A coloring composition comprising the triarylmethane dye according to any one of (1. to 8.).

[0031] 10. A colorant for a color filter, comprising the coloring composition described in (9.).

[0032] 11. A color filter using the colorant for color filter described in (10.).

[0033] The triarylmethane dye of the present invention has excellent heat resistance, and a coloring composition containing the dye is useful as a colorant for color filters. DETAILED DESCRIPTION

[0034] Hereinafter, the present invention will be described in detail based on the embodiments. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be implemented within the scope of the gist thereof. First, the triarylmethane coloring matter represented by the general formula (1) will be described.

[0035] In the general formula (1), as R 1 ~R 14Specifically, the “straight-chain, branched or cyclic alkyl group having 1 to 12 carbon atoms” in the “straight-chain, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent” includes straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl; isopropyl, isobutyl, sec-butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1- Branched alkyl groups such as methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-1-methylpropyl, isooctyl, and 2-ethylhexyl; cyclic alkyl groups (cycloalkyl groups) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl; norbornyl, 1-adamantyl, and 2-adamantyl. Here, the lower limit of the number of carbon atoms of the "branched or cyclic alkyl group" can be understood by those skilled in the art as the number of carbon atoms that can form a branched or cyclic structure (i.e., 3 carbon atoms).

[0036] In the general formula (1), as R 1 ~R 5 , R 11 ~R 14 Specifically, the “aromatic hydrocarbon group having 6 to 20 carbon atoms” in the “aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent” includes aromatic hydrocarbon groups such as phenyl, biphenyl, terphenyl, naphthyl, azulenyl, anthracenyl, naphthphenyl, phenanthrenyl, fluorenyl, indenyl, pyrene, perylenyl, fluoranthenyl and benzo[9,10]phenanthrenyl (the “aromatic hydrocarbon group” in the present invention also includes an aryl group or a condensed polycyclic aromatic group).

[0037] In the general formula (1), as R 1 ~R 5Specifically, the “heterocyclic group having 2 to 20 carbon atoms” in the “heterocyclic group having 2 to 20 carbon atoms which may have a substituent” represented by the formula (I) includes pyridyl, pyrimidinyl, quinolyl, isoquinolyl, pyrazinyl, triazinyl, naphthyridinyl, acridinyl, phenanthrolinyl, carbolinyl, purinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, phenanthridinyl, pyrimidinyl, oxadinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, dihydropyrrolopyrrolyl, indolyl, isoindolyl, indolizine, indazolyl, benzimidazolyl, benzotriazolyl, carbazolyl, azaindolyl, Heterocyclic groups (or heteroaromatic hydrocarbon groups) such as dolyl, azaindazolyl, pyrazolopyrimidinyl, adenosyl, guanidinyl, phenazinyl, furanyl, thienyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, dibenzofuranyl, dibenzothienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, furopyrrolyl, thienopyrrolyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzisothiazolyl, benzothiadiazolyl, phenoxathiol, oxazolopyridinyl, oxazolopyrazinyl, benzo[1,2-b:4,5-b']dithienyl and bipyridyl.

[0038] In the general formula (1), as R 6 ~R 10 The "halogen atom" represented by ' includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. The "halogen atom" is preferably a fluorine atom or a chlorine atom.

[0039] In the general formula (1), as R 6 ~R 10 Specifically, the “straight-chain, branched or cyclic alkoxy group having 1 to 12 carbon atoms” in the “straight-chain, branched or cyclic alkoxy group having 1 to 12 carbon atoms which may have a substituent” includes: straight-chain alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy; branched-chain alkoxy groups such as isopropoxy, isobutoxy, sec-butoxy, tert-butoxy and isooctyloxy; cyclic alkoxy groups (cycloalkoxy groups) such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy and cyclodecyloxy; 1-adamantyloxy and 2-adamantyloxy groups.

[0040] In the general formula (1), as R 1 ~R 14The “substituent” in the “straight-chain, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent”, “aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent”, “heterocyclic group having 2 to 20 carbon atoms which may have a substituent” or “straight-chain, branched or cyclic alkoxy group having 1 to 12 carbon atoms which may have a substituent” represented by any of the above may specifically include:

[0041] Deuterium atom, hydroxyl group (―OH), thiol group (―SH), cyano group (―CN), nitro group (―NO2), trifluoromethyl group (―CF3), carbonyl group (―(C=O)―);

[0042] Halogen atoms such as fluorine, chlorine, bromine, and iodine;

[0043] A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms;

[0044] A linear or branched alkenyl group having 2 to 20 carbon atoms;

[0045] A straight-chain or branched alkynyl group having 2 to 20 carbon atoms;

[0046] A linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms;

[0047] 1-adamantyloxy, 2-adamantyloxy;

[0048] Acyl groups having 1 to 20 carbon atoms;

[0049] An aromatic hydrocarbon group or a condensed polycyclic aromatic group having 6 to 20 carbon atoms;

[0050] A heterocyclic group having 2 to 20 carbon atoms;

[0051] An aryloxy group having 6 to 20 carbon atoms;

[0052] Unsubstituted amino group; mono- or di-substituted amino group having 1 to 20 carbon atoms;

[0053] -COOH, -COOM or a carbonyl group, an ester group or an amide group having 1 to 20 carbon atoms which may have a substituent;

[0054] -SO3H, -SO3M or a sulfonyl group or sulfonamide group having 0 to 20 carbon atoms which may have a substituent (wherein M represents an inorganic cation or an organic cation), etc.

[0055] For these "substituents", only one or more may be included, and in the case of including more than one, they may be the same or different from each other. In addition, in the group having these "substituents", for the position where the "substituent" is bonded, for example, when considering multiple positions such as any one of the 4 carbons in n-butyl, the para position, meta position, ortho position in phenyl, it can be substituted at any position, and when considering multiple positions that become bond arms such as pyridyl and naphthyl, the "substituent" can be bonded at any position. In addition, these "substituents" may further have the substituents exemplified above. Therefore, these “substituents” can also be represented by, for example, “a straight-chain or branched unsubstituted or substituted alkyl group having 1 to 20 carbon atoms,” “a straight-chain or branched unsubstituted or substituted alkenyl group having 2 to 20 carbon atoms,” “a straight-chain or branched alkynyl group having 2 to 20 carbon atoms,” “an unsubstituted or substituted cycloalkoxy group having 3 to 20 carbon atoms,” “an unsubstituted or substituted aryloxy group having 6 to 20 carbon atoms,” “an unsubstituted or substituted amino group having 0 to 20 carbon atoms,” “an unsubstituted or substituted amide group having 1 to 20 carbon atoms,” “an unsubstituted or substituted ammonium group having 0 to 20 carbon atoms,” “an unsubstituted or substituted phenyl group having 6 to 20 carbon atoms,” “an unsubstituted or substituted phenoxy group having 6 to 20 carbon atoms,” “a phenyl group having 6 to 20 carbon atoms substituted by a straight-chain or branched alkyl group having 1 to 20 carbon atoms substituted by a halogen atom,” and the like. It should be noted that when the "substituent" contains a carbon atom, the carbon atom is included in the above-mentioned "carbon atoms 1 to 20" and "carbon atoms 6 to 20". In addition, these substituents may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene, an oxygen atom or a sulfur atom to form a ring.

[0056] In the general formula (1), when there is a "mono- or di-substituted amino group having 1 to 20 carbon atoms", examples thereof include those represented by "-NR 15 R 16 "" has a substituent R 15 and R 16 The term "amino group" refers to a monosubstituted amino group, a disubstituted amino group, and the like.

[0057] In the case of "having a substituent R 15 and R 16 The amino group" is represented by R 15 and R 16 The "substituent" represented by R 1 ~R 14The "substituent" in each group represented is the same group. Examples of the monosubstituted amino group include ethylamino, butylamino, acetylamino, and phenylamino. Examples of the disubstituted amino group include dialkylamino groups having 2 to 20 carbon atoms, such as dimethylamino, diethylamino, dipropylamino, dibutylamino, and dihexylamino; diallylamino groups having 4 to 20 carbon atoms, such as diallylamino; diphenylamino, N-acetyl-N-phenylamino, and (n-butyl)-N-phenylamino.

[0058] In the general formula (1), when an "inorganic cation" or "organic cation" represented by "M" is present, examples of the "organic cation" include those represented by R. 17 R 18 R 19 R 20 N + The ammonium ion represented by the formula, R 17 ~R 20 Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and may be bonded to each other to form a ring. 17 ~R 20 The "substituent", "linear or branched alkyl group having 1 to 20 carbon atoms" and "aromatic hydrocarbon group having 6 to 20 carbon atoms" in the general formula (1) can be specifically applied to R 1 ~R 14 The same applies. In addition, examples of "inorganic cations" include alkali metal ions such as lithium ions and sodium ions, and alkaline earth metal ions such as magnesium ions, calcium ions, and barium ions. M is preferably an alkali metal ion.

[0059] In the general formula (1), when there is a "carbonyl group, ester group or amide group having 1 to 20 carbon atoms which may have a substituent", it refers to "-(C=O)-R 21 ”, “―(C=O)―O―R 21 " or "-(C=O)-NR 15 R 16 " represents a group. 21 and “-NR 15 R 16 "Can be applied to the 1 ~R 14 The "substituent" in each group represented has the same meaning.

[0060] In the general formula (1), when there is a "sulfonyl group or sulfonamide group having 0 to 20 carbon atoms which may have a substituent", it means "-SO2-R 21” (or “―S(=O)2―R 21 ”) or “―S(=O)2―NR 15 R 16 " represents a group. 21 and “-NR 15 R 16 "Can be applied to the 1 ~R 14 The "substituent" in each group represented has the same meaning.

[0061] It should be noted that, for the compound represented by R in the general formula (1), 1 ~R 14 The "substituent" represented by the above-mentioned various "groups" includes "linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms",

[0062] "a linear or branched alkenyl group having 2 to 20 carbon atoms",

[0063] "a linear or branched alkynyl group having 2 to 20 carbon atoms",

[0064] "a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms",

[0065] "Acyl group having 1 to 20 carbon atoms",

[0066] "an aromatic hydrocarbon group or a condensed polycyclic aromatic group having 6 to 20 carbon atoms",

[0067] "a heterocyclic group having 2 to 20 carbon atoms",

[0068] Specific examples of the “aryloxy group having 6 to 20 carbon atoms” or the “mono- or di-substituted amino group having 1 to 20 carbon atoms” include:

[0069] Straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, heptyl, octyl, isooctyl, nonyl, and decyl;

[0070] Cyclic alkyl groups (cycloalkyl groups) such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl and cyclodecyl;

[0071] an alkenyl group such as vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, isobutenyl, or a linear or branched alkenyl group in which a plurality of these alkenyl groups are bonded;

[0072] Alkynyl groups such as ethynyl, propargyl, butynyl, or linear or branched alkynyl groups formed by bonding a plurality of these alkynyl groups; mixed groups of alkenyl and alkynyl groups such as pent-3-en-1-ynyl and hex-2-en-4-ynyl;

[0073] Straight-chain or branched alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy and isooctyloxy;

[0074] Cyclic alkoxy groups having 3 to 20 carbon atoms (cycloalkoxy groups) such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy and cyclodecyloxy;

[0075] Acyl groups such as formyl, acetyl, propionyl, acryloyl, benzoyl, etc.

[0076] Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as phenyl, biphenyl, terphenyl, naphthyl, anthracenyl (anthryl), naphthacene, phenanthrenyl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, and benzo[9,10]phenanthrenyl;

[0077] Heterocyclic groups such as thienyl, furanyl, pyrrolyl, thiazolyl, oxazolyl, imidazolyl, pyrazolyl, triazolyl, benzothienyl, benzofuranyl, indolyl, isoindolyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzotriazolyl, purinyl, carbazolyl, dibenzothienyl, dibenzofuranyl, pyridyl, pyrimidinyl, triazine, bipyridyl, quinolyl, isoquinolyl, naphthyridinyl, acridinyl, phenanthrolinyl and carbolyl;

[0078] Aryloxy groups such as phenoxy, tolyloxy, biphenyloxy, naphthoxy, anthryloxy, and phenanthrenoxy;

[0079] Aralkyloxy groups such as benzyl and phenethyl;

[0080] Straight-chain or branched monoalkylamino groups such as methylamino, ethylamino, isopropylamino, etc.; straight-chain or branched dialkylamino groups such as dimethylamino, diethylamino, ethylmethylamino, dipropylamino, dibutylamino, di(2-ethylhexyl)amino, di-tert-butylamino, etc.; monoarylamino groups such as phenylamino, 1-naphthylamino, 2-naphthylamino, etc.; diarylamino groups such as diphenylamino, N-phenyl-1-naphthylamino, etc.; alkylarylamino groups such as N-methyl-phenylamino, etc.; other straight-chain or branched alkyl groups, or mono-substituted or di-substituted amino groups having aromatic hydrocarbon groups, etc.

[0081] As R in the general formula (1) 1 and R 3, preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and particularly preferably a phenyl group or a naphthyl group which may have a substituent. 1 and R 3 They may be the same or different from each other, but are preferably the same.

[0082] As R in the general formula (1) 2 and R 4 , preferably -H, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, more preferably -H, or a linear, branched or cyclic alkyl group having 1 to 3 carbon atoms which may have a substituent.

[0083] As R in the general formula (1) 5 , preferably -H, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, more preferably a linear, branched or cyclic alkyl group having 1 to 3 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, particularly preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0084] In the general formula (1), R 5 When there is a substituent, the substituent is preferably a cyano group (-CN), a nitro group (-NO2), a trifluoromethyl group (-CF3), a carbonyl group (-(C=O)-), a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably an electron-withdrawing group such as a nitro group (-NO2), a trifluoromethyl group (-CF3), a halogen atom, etc.

[0085] As R in the general formula (1) 8 , R 12 ~R 14 , preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, more preferably a linear alkyl group having 1 to 3 carbon atoms which may have a substituent. 6 , R 7 , R 9 ~R 11 , each independently as defined above, but preferably all are hydrogen. In a particularly preferred embodiment, the triarylmethane pigment is R in the general formula (1): 11H, R 8 , R 12 ~R 14 A compound having a linear alkyl group having 1 to 3 carbon atoms which may have a substituent.

[0086] In the general formula (1), An is not particularly limited, and examples thereof include halogen compound ions and organic anions. Specifically, examples thereof include:

[0087] Cl - Br - ,I - ;(CF3SO2)2N - (or Tf2N - ),

[0088] (CF3SO2)3C - (or Tf3C - ),

[0089] (C2F5SO2)2N - 、(C4F9SO2)2N - 、(C6F5SO2)2N - ,

[0090] (C2F5)3F3P - ,

[0091] (CN)2N - 、(CN)3C - , NC-S - ,;

[0092] (C6H4SO3 - )O(C6H3(C 12 H 25 )(SO3 - ))、

[0093] C6H4(C 12 H 25 )(SO3 - );PF6 - 、BF4 - ;

[0094] (PW 12 O 40 ) 3- 、(P2W 18 O 62 ) 6- ,

[0095] (SiW 12 O 40 ) 4- 、(PMo 12 O40 ) 3- 、(SiMo 12 O 40 ) 3- ,

[0096] (PW 12-x Mo x O 40 ) 3- 、(SiW 12-x Mo x O 40 ) 4- ,

[0097] (P2W 18-y Mo y O 40 ) 6- (x represents an integer of 1 to 11, y represents an integer of 1 to 17) or the like heteropolyacid anions;

[0098] Or anions represented by the following structural formulas (Z-1) to (Z-16), etc.

[0099]

Chemical formula 2

[0100]

[0101]

Chemical formula 3

[0102]

[0103]

Chemical formula 4

[0104]

[0105]

Chemical formula 5

[0106]

[0107] In the general formula (1), An can be a single ion or a combination of two or more different ions, preferably a single ion selected from the anions exemplified above or any combination of two or three ions, and further preferably a single ion selected from any one of perfluoroalkylsulfonic acid anions (more preferably perfluoroalkylsulfonic acid anions having 1 to 24 carbon atoms), perfluoroalkylsulfonyl imide anions (more preferably perfluoroalkylsulfonyl imide anions having 1 to 24 carbon atoms), tris(trifluoromethanesulfonyl) methide anions or heteropolyacid anions or any combination of two or three ions. Therefore, "m" in the general formula (1) is an arbitrary natural number selected based on the valence of [An] as a whole in the formula (1) and the valence of the cation of the triarylmethane skeleton structure in [] so that the formula (1) as a whole is electrically neutral. m is preferably an integer of 1 to 6, more preferably an integer of 1 to 3.

[0108] Specific examples of preferred compounds of the triarylmethane dye of the present invention represented by the general formula (1) are shown below, but the present invention is not limited to these compounds. The following formulas (B-1) to (B-24) represent the triarylmethane dye portion in the general formula (1) with the anion portion represented by [An] omitted. In the following structural formula, a planar structural formula is described in which some hydrogen atoms are omitted and all stereoisomers and tautomers that can be generated are included.

[0109]

Chemical formula 6

[0110]

[0111]

Chemical formula 7

[0112]

[0113]

Chemical formula 8

[0114]

[0115]

Chemical formula 9

[0116]

[0117]

Chemical formula 10

[0118]

[0119]

Chemical formula 11

[0120]

[0121]

Chemical formula 12

[0122]

[0123]

Chemical formula 13

[0124]

[0125] The method for producing the triarylmethane pigment represented by the general formula (1) is not particularly limited, and the known method (e.g., non-patent document 1) can be applied and the reagents or other appropriate reagents having various corresponding groups of the general formula (1) can be used to produce the triarylmethane pigment. Hereinafter, a method for producing the compound of the present invention is described. However, the present invention is not limited thereto.

[0126] The triarylmethane dye represented by the general formula (1) is obtained by subjecting a benzophenone derivative having a corresponding substituent to a condensation reaction with a tetrahydroquinoline having a corresponding substituent. Furthermore, the triarylmethane dye represented by the general formula (1) can be produced by salt exchange with a salt having a corresponding structure as required. The chemical reaction in the production can be carried out in the presence of an organic solvent or in the absence of a solvent.

[0127] The separation and purification of each product in the production method of the present invention can be appropriately combined with the methods used in conventional organic synthesis, such as: purification by column chromatography; adsorption purification by silica gel, activated carbon, activated clay, etc.; known methods such as recrystallization and crystallization using solvents. In addition, in the identification, analysis, optical properties, thermophysical properties, and evaluation of other physical properties of these compounds, nuclear magnetic resonance analysis (NMR), absorbance measurement using a spectrophotometer, ultraviolet visible absorption spectrum (UV-Vis) measurement, thermogravimetric measurement-differential thermal analysis (TG-DTA), etc. can be performed. These analytical methods can also be used in the solubility, color evaluation, and heat resistance evaluation of the obtained compounds.

[0128] The triarylmethane pigment of the present invention can be used alone or in combination (e.g., mixed) of two or more different molecular structures. When using the two or more triarylmethane pigments, the mass concentration ratio of the least triarylmethane pigment in the total triarylmethane pigment is 0.1 mass % to 50 mass %. The type of triarylmethane pigment is preferably one or two.

[0129] The triarylmethane colorant of the present invention, the coloring composition containing the colorant, and the color filter colorant containing the colorant or the coloring composition need to be well dissolved or dispersed in an organic solvent containing a resin or the like in the production process of the colorant and the color filter, and therefore, it is preferred that the solubility and dispersibility in the organic solvent be high. The organic solvent is not particularly limited, and specifically, examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as propylene glycol monomethyl ether acetate (PGMEA), methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether (PGME); ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and 3-heptanone; alcohols such as methanol, ethanol, 2-propanol, and propylene glycol; esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, ethyl acetate, butyl acetate, and methyl 3-methoxypropionate; diacetone alcohol (DAA) and the like; amides such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO), and the like are preferred. PGME, PGMEA, cyclohexanone, or DAA is preferred, and PGME or PGMEA is particularly preferred from the viewpoint of balancing the solubility of the resin and the solubility of the triarylmethane dye. These solvents may be used alone or in combination of two or more.

[0130] For the triarylmethane pigment of the present invention, the maximum absorption wavelength showing the maximum absorbance in the visible light region (e.g., wavelength range of 350nm to 800nm) of the ultraviolet-visible absorption spectrum measured near room temperature (e.g., 23°C to 27°C) using a solution prepared by dissolving it in an organic solvent is observed. In the present invention, the maximum absorption wavelength in the PGME solution is preferably a wavelength range of 570nm to 640nm. It should be noted that the pigment concentration is preferably 0.005mmol / L to 0.02mmol / L. The solvent is not limited as long as it is a solvent that dissolves the pigment, but it is preferably a solvent that does not greatly shift the absorption wavelength of the ultraviolet-visible absorption spectrum due to the dissolution conditions, preferably PGME.

[0131] By mixing the triarylmethane dye of the present invention with various resin solutions and applying the mixture on a glass substrate, a coating film can be prepared. The obtained coating film is measured using a spectrophotometer to obtain the color value of the coating film, thereby enabling color evaluation. Color values ​​are generally measured using CIE L ＊ a ＊ b ＊ Specifically, the color value L of the film sample can be measured. ＊ 、a ＊ 、b ＊ , the color difference (ΔE ＊ ab) to judge heat resistance. In the case of application to color filters, the color difference at a temperature of about 230°C can be used as an indicator of heat resistance. ＊ ab For example, the smaller the value, the less discoloration caused by thermal decomposition and the higher the heat resistance, preferably 20 or less, more preferably 12 or less, and further preferably 10 or less. In addition, as a comparison method for the heat resistance of the pigment, it can be evaluated by thermogravimetric measurement, for example, a thermogravimetric measurement-differential thermal analysis device can be used to measure the 5% mass reduction temperature by thermogravimetric measurement under an inert gas atmosphere such as nitrogen. As the 5% mass reduction temperature, it is preferably 270°C or more, more preferably 300°C or more, and the higher the decomposition temperature, the better.

[0132] The colorant for color filter of the present invention comprises a triarylmethane pigment represented by general formula (1) or a coloring composition containing at least one triarylmethane pigment and components commonly used in the manufacture of color filter. For a common color filter, for example, in the case of a method utilizing a photolithography process, it is obtained by the following method: a pigment such as a dye, a pigment, a resin component (including a monomer, an oligomer), and a solvent are mixed, and the prepared liquid is applied to a substrate of glass, a resin, etc., and it is exposed through a photomask to make a coloring pattern of a pigment-resin composite film soluble / insoluble in the solvent, and after washing, it is heated. In addition, in an electrodeposition method or a printing method, a mixture obtained by mixing a pigment with a resin and other components is also used to make a coloring pattern. Therefore, as specific components in the colorant for color filter of the present invention, it can be listed: at least one triarylmethane pigment represented by general formula (1), other pigments such as dyes, pigments, resin components, organic solvents, and other additives such as photopolymerization initiators. In addition, it is possible to select from these components, and it is also possible to add other components as needed.

[0133] When the triarylmethane dye of the present invention or a coloring composition containing the triarylmethane dye is used as a colorant for color filters, it can be used for color filters of various colors, but is preferably used as a colorant for blue or green color filters.

[0134] The colorant for color filter of the present invention may be used alone or two or more triarylmethane dyes may be mixed with known dyes such as other dyes and pigments in order to adjust the color tone, that is, to adjust the spectral characteristics.

[0135] When used as a colorant for a blue color filter, there is no particular limitation, and examples thereof include basic dyes such as CI Basic Blue 3, CI Basic Blue 7, CI Basic Blue 9, CI Basic Blue 54, CI Basic Blue 65, CI Basic Blue 75, CI Basic Blue 77, CI Basic Blue 99, CI Basic Blue 129, and CI Basic Violet 10; acid dyes such as CI Acid Blue 9, CI Acid Blue 74, CI Acid Red 52, and CI Acid Red 289; disperse dyes such as Disperse Blue 3, Disperse Blue 7, and Disperse Blue 377; spiroketone dyes; cyanine-based, indigo-based, phthalocyanine-based, anthraquinone-based, methine-based, triarylmethane-based, indanthrene-based, oxazine-based, dioxazine-based, azo-based, and xanthene-based pigments; and other blue-based lake pigments and other blue or red-based dyes or pigments.

[0136] When used as a colorant for a green color filter, there is no particular limitation, and examples thereof include green pigments such as CI Pigment Green 7, CI Pigment Green 10, CI Pigment Green 36, CI Pigment Green 47, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 62, and CI Pigment Green 63; yellow pigments such as CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, and CI Pigment Yellow 185; spiroketone dyes; cyanine-based, indigo-based, phthalocyanine-based, anthraquinone-based, methine-based, triarylmethane-based, indanthrene-based, oxazine-based, dioxazine-based, azo-based, xanthene-based, isoindoline-based, and quinophthalone-based pigments; and other blue, yellow, or green dyes or pigments such as lake pigments.

[0137] In the present invention, as a pigment mixed for adjusting the color tone, when used as a colorant for a blue color filter, triarylmethane-based pigments not belonging to the present invention such as CI Basic Blue 7; xanthene-based pigments such as CI Basic Violet 10, CI Acid Red 52, and CI Acid Red 289; phthalocyanine-based pigments such as CI Pigment Blue 15:3; or dioxazine-based pigments such as CI Pigment Violet 23 are preferred. When used as a colorant for a green color filter, quinophthalone-based pigments such as CI Pigment Yellow 138, isoindoline-based pigments such as CI Pigment Yellow 185, azo pigments such as CI Pigment Yellow 150, or phthalocyanine-based pigments such as CI Pigment Green 58 are preferred. By using these pigments and the triarylmethane pigment belonging to the present invention, a blue or green color filter can be obtained that is easy to optimize the transmission spectrum and has excellent light resistance and chemical resistance.

[0138] The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, grafting treatment on the pigment surface using a polymer compound, micronization treatment using a sulfuric acid micronization method, or washing treatment using an organic solvent or water for removing impurities, or removal treatment of ionic impurities using an ion exchange method, etc. It is preferred that the particle size of each pigment be uniform.

[0139] The mixing ratio of other pigments in the colorant for color filter of the present invention is preferably 5% by mass to 2000% by mass, and more preferably 10% by mass to 1000% by mass, relative to the triarylmethane pigment (the total of the two or more). The mixing ratio of pigment components such as dyes in the liquid color filter colorant is preferably 0.5% by mass to 70% by mass, and more preferably 1% by mass to 50% by mass, relative to the entire colorant.

[0140] As the resin component in the colorant for color filter of the present invention, as long as it is a resin component having the properties required for the manufacturing method and use of the color filter resin film formed by using these components, a known resin component can be used. Specifically, for example, acrylic resins, olefin resins, styrene resins, polyimide resins, polyurethane resins, polyester resins, epoxy resins, vinyl ether resins, phenolic (novolac) resins, other transparent resins, photocurable resins or thermosetting resins can be listed, and the monomers or oligomer components of these components can be appropriately combined. In addition, copolymers of the resins of these components can also be used in combination. In the case of liquid colorants, the content of the resins of these components in the colorant for color filter is preferably 5% by mass to 95% by mass, and more preferably 10% by mass to 50% by mass.

[0141] In order to improve the performance as a colorant for color filters, the coloring composition of the present invention may add surfactants, dispersants, defoamers, leveling agents, antioxidants, ultraviolet absorbers, other additives mixed during the manufacture of colorants for color filters, and other organic compounds as other components of the compound. However, it is preferred that the content of these additives in the coloring composition is appropriate, preferably a content that reduces or increases the solubility of the coloring composition of the present invention in the solvent to a level greater than required and does not affect the effects of other additives of the same type used in the manufacture of color filters. These additives can be added at any time when preparing the coloring composition.

[0142] As other additives in the colorant for color filter of the present invention, the components required for polymerization and curing of resins such as photopolymerization initiators and crosslinking agents can be listed. In addition, surfactants and dispersants required for stabilizing the properties of the components in the liquid colorant for color filter can be listed. These additives can all use known additives for color filter manufacturing, and are not particularly limited. The mixing ratio of the total amount of these additives in the solid content of the colorant for color filter is preferably 5% by mass to 60% by mass, and more preferably 10% by mass to 40% by mass.

[0143] Example

[0144] Hereinafter, the embodiments of the present invention will be specifically described using examples, but the present invention is not limited to the following examples. The reagents described in the synthesis examples are products manufactured by Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Co., Ltd., Alfa Aesar Co., Ltd., Duksan Co., Ltd., Daejung Co., Ltd., etc. In addition, the reactions in the synthesis examples are all carried out in a reaction container equipped with a condenser, a stirring device, and a thermometer, and are carried out under a nitrogen gas flow unless otherwise specified. It should be noted that the identification of the compounds in the following synthesis examples is carried out using 1 H-NMR analysis was performed using a nuclear magnetic resonance apparatus manufactured by Bruker Corporation, model: Ascend (registered trademark) 400 MHz.

[0145] [Synthesis Example 1] Synthesis of Compound (C-1)

[0146] 40.0 g (211 mmol) of 1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline, 65.9 g (423 mmol) of ethane, 52.6 g (380 mmol) of potassium carbonate, and 160 mL of DMF were added to a reaction container, and the mixture was stirred at 75°C for 7 hours. After cooling, 200 mL of ethyl acetate and 200 mL of heptane were added to the reaction solution, and the mixture was stirred at room temperature (23°C to 28°C), and then filtered. 300 mL of water was added to the filtrate, and the organic layer was extracted. After further washing with 300 mL of water twice, the organic layer was extracted. Anhydrous magnesium sulfate was added, the organic layer was dried, filtered, and the filtrate was concentrated under reduced pressure. After the residue was dissolved in 350 mL of heptane, 45 g of silica gel was added, and the mixture was stirred at room temperature for 30 minutes, and then filtered. The filtrate was concentrated under reduced pressure to obtain the following (Intermediate 100) (42.5 g, yield 92%).

[0147]

Chemical formula 14

[0148]

[0149] Next, 5.60 g (25.8 mmol) of the (intermediate 100), 8.36 g (25.8 mmol) of 4,4'-bis(diethylamino)benzophenone, and 30 mL of toluene were added to the reaction container, and stirred at room temperature (23°C to 28°C). 5.01 g (51.5 mmol) of phosphorus oxychloride was added dropwise thereto, and stirred at 100°C for 5 hours. After the reaction solution was cooled to room temperature, 50 mL of dichloromethane and 50 mL of water were added to extract the organic layer. Anhydrous magnesium sulfate was added, the organic layer was dried, filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane / methanol = 100 / 0 to 90 / 10 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 60°C to obtain the following (intermediate 101) (13.1 g, yield 91%).

[0150]

Chemical formula 15

[0151]

[0152] Next, 3.48 g (6.21 mmol) of the intermediate 101 and 50 mL of methanol were added to the reaction container. After the solid was dissolved, a solution obtained by dissolving 8.49 g of phosphotungstic acid hydrate in 100 mL of methanol was added dropwise. The solution was stirred at 40° C. for 4 hours, and the reaction solution was filtered. The obtained solid was suspended and washed with 100 mL of methanol, and after filtering the solid, it was dried under reduced pressure at 60° C., thereby obtaining a blue solid (8.30 g, yield 92%) of the target compound (C-1).

[0153] The obtained blue solid was subjected to NMR measurement, and the following 150 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (C-1).

[0154] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.24 (12H), 6.98 (12H), 6.83 (3H), 6.66 (3H), 3.6 1(30H), 2.84(3H), 1.86(3H), 1.50(3H), 1.42(9H), 1.28(9H), 1.19(54H), 1.13(9H).

[0155]

Chemical formula 16

[0156]

[0157] [Synthesis Example 2] Synthesis of Compound (C-2)

[0158] 25.0 g (132 mmol) of 1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline, 24.9 g (145 mmol) of 4-bromotoluene, 22.2 g (198 mmol) of potassium tert-butoxide, 88 mL of toluene, 1.48 g (6.60 mmol) of palladium acetate, and 5.34 g (13.2 mmol) of tri-tert-butylphosphine (50 wt% toluene solution) were added to a reaction vessel, and the mixture was stirred under reflux for 72 hours. After cooling, the reaction solution was filtered, and the filtrate was washed with 200 mL of water to extract the organic layer. Anhydrous magnesium sulfate was added, the organic layer was dried, filtered, and the filtrate was concentrated under reduced pressure. The residue was dissolved in 350 mL of heptane, 35 g of silica gel was added, and the mixture was stirred at room temperature (23°C to 28°C) for 30 minutes, and then filtered. The filtrate was concentrated under reduced pressure to obtain the following (Intermediate 102) (34.6 g, yield 94%).

[0159]

Chemical formula 17

[0160]

[0161] Add 49.1 g (458 mmol) of N-methylaniline and 175 mL of N,N-dimethylformamide (DMF) to a reaction container and cool to 5°C while stirring. Add 51.4 g (458 mmol) of potassium tert-butoxide to the solution in four portions. Further, add dropwise a solution obtained by dissolving 25.0 g (114 mmol) of 4,4'-difluorobenzophenone in 100 mL of DMF. After the addition, warm to room temperature and stir for 3 hours. Pour the reaction solution into 600 mL of water and filter out the precipitated solid. Add the obtained solid to 200 mL of methanol, perform suspension washing at room temperature, and filter out the solid. The obtained solid is dried under reduced pressure at 60°C to obtain the following (Intermediate 103) (42.7 g, yield 95%).

[0162]

Chemical formula 18

[0163]

[0164] Next, in the synthesis of (Intermediate 101) in Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 102) and 4,4'-bis(diethylamino)benzophenone was changed to (Intermediate 103), the following (Intermediate 104) (8.69 g, yield 99%) was obtained by the same method.

[0165]

Chemical formula 19

[0166]

[0167] Next, 3.50 g (5.07 mmol) of the (intermediate 104) and 17 mL of methanol were added to the reaction vessel, stirred, and after the solid was dissolved, 1.53 g (5.32 mmol) of lithium bis(trifluoromethanesulfonyl)imide (LiN(SO2CF3)2) was added. After stirring at 45°C for 1 hour, the mixture was cooled, 85 mL of water was added, and the precipitated solid was filtered out. The obtained solid was dried under reduced pressure at 80°C to obtain the target compound (C-2) as a purple solid (4.31 g, yield 91%).

[0168] The obtained purple solid was subjected to NMR measurement, and the following 48 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (C-2).

[0169] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.58 (4H), 7.41 (8H), 7.24 (4H), 7.16 (1H), 7.12 (1H), 6.97 (1H), 6.92 (4H) , 5.82(1H), 3.52(6H), 3.06(1H), 2.40(3H), 2.02(1H), 1.71(1H), 1.53(3H), 1.34(3H), 1.23(3H), 1.07(3H).

[0170]

Chemical formula 20

[0171]

[0172] [Synthesis Example 3] Synthesis of Compound (C-3)

[0173] In the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 101) was replaced by the above-mentioned (Intermediate 104), the target compound (C-3) was obtained as a blue-purple solid (6.06 g, yield 91%) by the same method.

[0174] The obtained blue-purple solid was subjected to NMR measurement, and the following 144 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (C-3).

[0175] 1H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.58 (12H), 7.41 (24H), 7.24 (12H), 7.16 (3H), 7.13 (3H), 6.98 (3H), 6.93 (12 H), 5.82(3H), 3.52(18H), 3.06(3H), 2.40(9H), 2.02(3H), 1.72(3H), 1.52(9H), 1.34(9H), 1.23(9H), 1.07(9H).

[0176]

Chemical formula 21

[0177]

[0178] [Synthesis Example 4] Synthesis of Compound (C-4)

[0179] 4,4'-dichlorobenzophenone 35.0g (139mmol), 2,6-dimethylaniline 33.8g (279mmol), sodium tert-butoxide 37.5g (390mmol) and xylene 280mL were added to the reaction container, and palladium acetate 1.56g (6.97mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos) 6.64g (13.9mmol) were added while stirring at room temperature, and stirred at 110°C for 3 hours. The reaction solution was cooled to room temperature, and 200mL of water and 50mL of isopropanol were added, stirred, and the solid was filtered out. The obtained solid was suspended and washed with 200mL of water, and the solid was filtered out. The obtained solid was dried under reduced pressure at 80°C to obtain the following (Intermediate 105) (55.0g, yield 94%).

[0180]

Chemical formula 22

[0181]

[0182] Next, the following (Intermediate 106) (27.3 g, yield 88%) was obtained by the same method except that 4-bromotoluene was replaced with bromobenzene in the synthesis of (Intermediate 102) in Synthesis Example 2.

[0183]

Chemical formula 23

[0184]

[0185] Next, in the synthesis of (Intermediate 101) in Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 106) and 4,4'-bis(diethylamino)benzophenone was changed to (Intermediate 105), the following (Intermediate 107) (5.10 g, yield 76%) was obtained by the same method.

[0186]

Chemical formula 24

[0187]

[0188] Next, in the synthesis of compound (C-2) of Synthesis Example 2, except that (Intermediate 104) was replaced by the above-mentioned (Intermediate 107), the target compound (C-4) was obtained as a purple solid (5.10 g, yield 76%) by the same method.

[0189] The obtained purple solid was subjected to NMR measurement, and the following 49 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (C-4).

[0190] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 9.55 (2H), 7.58 (2H), 7.50 (1H), 7.35-7.09 (16H), 6.94 (1H), 5 .75(1H), 3.07(1H), 2.15(12H), 2.00(1H), 1.72(1H), 1.51(3H), 1.34(3H), 1.25(3H), 1.12(3H).

[0191]

Chemical formula 25

[0192]

[0193] [Synthesis Example 5] Synthesis of Compound (C-5)

[0194] Add 150 g (357 mmol) of the (intermediate 105) and 500 mL of DMF to a reaction vessel, and cool to 5°C while stirring. Add 120 g (1.07 mol) of potassium tert-butoxide to the solution in four portions, and then add 167 g (1.07 mol) of iodoethane dropwise while maintaining the temperature at 5°C. After the addition, raise the temperature to 35°C and stir for 3 hours. Add the reaction solution dropwise to 3.0 L of a 10% aqueous sodium chloride solution, and filter out the precipitated solid. After suspending and washing the obtained solid with 1.5 L of water, filter out the solid. After suspending and washing the obtained solid with a mixed solvent of 500 mL of water and 1.0 L of methanol, filter out the solid. The obtained solid is dried under reduced pressure at 80°C to obtain the following (intermediate 108) (152 g, yield 89%).

[0195]

Chemical formula 26

[0196]

[0197] Next, in the synthesis of (Intermediate 101) in Synthesis Example 1, except that 4,4′-bis(diethylamino)benzophenone was replaced by the above (Intermediate 108), the following (Intermediate 109) (14.1 g, yield 98%) was obtained in the same manner.

[0198]

Chemical formula 27

[0199]

[0200] Next, in the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 101) was replaced by the above-mentioned (Intermediate 109), the target compound (C-5) was obtained as a blue solid (13.7 g, yield 79%) by the same method.

[0201] The obtained blue solid was subjected to NMR measurement, and the following 174 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (C-5).

[0202] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.36 (6H), 7.33-7.19 (24H), 7.08 (6H), 6.83 (3H), 6.69 (3H), 6.03 (6H), 3.83 (12H), 3 .68(3H), 3.46(3H), 2.80(3H), 2.10(36H), 1.85(3H), 1.77(9H), 1.48(3H), 1.41(9H), 1.37(9H), 1.22(27H), 1.12(9H).

[0203]

Chemical formula 28

[0204]

[0205] [Synthesis Example 6] Synthesis of Compound (C-6)

[0206] In the synthesis of (Intermediate 101) of Synthesis Example 1, the (Intermediate 100) was changed to 1-(2-hydroxyethyl)-1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline, and 4,4'-bis(diethylamino)benzophenone was changed to the (Intermediate 108). Except for this, the following (Intermediate 110) (6.81 g, yield 85%) was obtained by the same method.

[0207]

Chemical formula 29

[0208]

[0209] Next, in the synthesis of compound (C-2) of Synthesis Example 2, except that (Intermediate 104) was replaced by the above-mentioned (Intermediate 110), the target compound (C-6) was obtained as a blue-purple solid (7.98 g, yield 87%) by the same method.

[0210] The obtained blue-purple solid was subjected to NMR measurement, and the following 57 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (C-6).

[0211] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.40 (2H), 7.29 (8H), 7.12 (2H), 6.84 (1H), 6.67 (1H), 6.05 (2H), 3.99 -3.56(8H), 2.83(1H), 2.11(12H), 1.88(1H), 1.76(3H), 1.48(1H), 1.40(3H), 1.31-1.16(9H), 1.13(3H).

[0212]

Chemical formula 30

[0213]

[0214] [Synthesis Example 7] Synthesis of Compound (C-7)

[0215] In the synthesis of (Intermediate 101) in Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 102) and 4,4'-bis(diethylamino)benzophenone was changed to (Intermediate 108), the following (Intermediate 111) (8.82 g, yield 74%) was obtained by the same method.

[0216]

Chemical formula 31

[0217]

[0218] Next, in the synthesis of compound (C-2) of Synthesis Example 2, except that (Intermediate 104) was replaced by the above-mentioned (Intermediate 111), the target compound (C-7) was obtained as a blue-purple solid (9.77 g, yield 85%) by the same method.

[0219] The obtained blue-purple solid was subjected to NMR measurement, and the following 60 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (C-7).

[0220] 1H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.38 (4H), 7.26 (8H), 7.28-7.13 (4H), 6.94 (1H), 6.05 (2H), 5.80 (1H), 3 .82(4H), 3.05(1H), 2.40(3H), 2.09(12H), 2.01(1H), 1.70(1H), 1.49(3H), 1.33(3H), 1.30(9H), 1.14(3H).

[0221]

Chemical formula 32

[0222]

[0223] [Synthesis Example 8] Synthesis of Compound (C-8)

[0224] In the synthesis of compound (C-1) of Synthesis Example 1, except that (Intermediate 101) was replaced by the above-mentioned (Intermediate 111), the target compound (C-8) was obtained as a blue solid (9.77 g, yield 85%) by the same method.

[0225] The obtained blue solid was subjected to NMR measurement, and the following 180 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (C-8).

[0226] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.38 (12H), 7.26 (24H), 7.28-7.13 (12H), 6.94 (3H), 6.05 (6H), 5.80 (3H), 3 .82(12H), 3.05(3H), 2.40(9H), 2.09(36H), 2.01(3H), 1.70(3H), 1.49(9H), 1.33(9H), 1.30(27H), 1.14(9H).

[0227]

Chemical formula 33

[0228]

[0229] [Synthesis Example 9] Synthesis of Compound (C-9)

[0230] In the synthesis of (Intermediate 101) in Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 106) and 4,4'-bis(diethylamino)benzophenone was changed to (Intermediate 108), the following (Intermediate 112) (9.02 g, yield 90%) was obtained by the same method.

[0231]

Chemical formula 34

[0232]

[0233] Next, in the synthesis of compound (C-2) of Synthesis Example 2, except that (Intermediate 104) was replaced by the above-mentioned (Intermediate 112), the target compound (C-9) was obtained as a blue-purple solid (10.0 g, yield 84%) by the same method.

[0234] The obtained blue-purple solid was subjected to NMR measurement, and the following 58 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (C-9).

[0235] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.59 (2H), 7.50 (1H), 7.38 (2H), 7.28 (10H), 7.11 (2H), 6.95 (1H), 6.05 (2H) , 5.76(1H), 3.82(4H), 3.06(1H), 2.09(12H), 2.01(1H), 1.72(1H), 1.43(3H), 1.35(3H), 1.20(9H), 1.14(3H).

[0236]

Chemical formula 35

[0237]

[0238] [Synthesis Example 10] Synthesis of Compound (C-10)

[0239] The following (Intermediate 113) (2.19 g, yield 45%) was obtained by the same method except that 4-bromotoluene was replaced with 1-bromo-4-nitrobenzene in the synthesis of (Intermediate 102) in Synthesis Example 2.

[0240]

Chemical formula 36

[0241]

[0242] Next, in the synthesis of (Intermediate 101) in Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 113) and 4,4'-bis(diethylamino)benzophenone was changed to (Intermediate 108), the following (Intermediate 114) (1.91 g, yield 33%) was obtained by the same method.

[0243]

Chemical formula 37

[0244]

[0245] Next, in the synthesis of compound (C-2) of Synthesis Example 2, except that (Intermediate 104) was replaced by the above-mentioned (Intermediate 114), the target compound (C-10) was obtained as a blue-purple solid (2.12 g, yield 85%) by the same method.

[0246] The obtained blue-purple solid was subjected to NMR measurement, and the following 57 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (C-10).

[0247] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.40 (2H), 7.55 (2H), 7.41 (2H), 7.29 (9H), 7.14 (2H), 6.98 (1H), 6.06 (2H), 3.84(4H), 3.08(1H), 2.09(12H), 2.02(1H), 1.74(1H), 1.51(3H), 1.35(3H), 1.21(9H), 1.11(3H).

[0248]

Chemical formula 38

[0249]

[0250] [Synthesis of Comparative Example Compound (D-1)]

[0251] By the method described in paragraph

[0067] Example 2 of Patent Document 2 (Japanese Patent Application Laid-Open No. 2011-186043), a dark blue solid of Comparative Example Compound (D-1) represented by the following formula was obtained.

[0252] The obtained dark blue solid was subjected to NMR measurement, and the following 120 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (D-1).

[0253] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.34 (3H), 8.02 (3H), 7.60-7.11 (24H), 6.94 (12H), 6.81 (3H), 3.58 (30H), 1.34 (9H), 1.20 (36H).

[0254]

Chemical formula 39

[0255]

[0256] [Synthesis of Comparative Example Compound (D-2)]

[0257] By the method described in paragraph

[0058] Synthesis Example 1 of Patent Document 3 (Japanese Patent Application Laid-Open No. 2012-83652), a brown solid of a comparative example compound (D-2) represented by the following formula was obtained.

[0258] The obtained brown solid was subjected to NMR measurement, and the following 40 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (D-2).

[0259] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.34 (1H), 8.02 (1H), 7.60-7.11 (8H), 6.94 (4H), 6.81 (1H), 3.58 (10H), 1.34 (3H), 1.20 (12H).

[0260]

Chemical formula 40

[0261]

[0262] [Synthesis of Comparative Example Compound (D-3)]

[0263] 5.00 g (25.9 mmol) of 4-diethylaminobenzoic acid and 30 mL of toluene were added to a reaction container, and 4.62 g (38.8 mmol) of thionyl chloride was added, and the mixture was stirred at 80°C for 1 hour. After the reaction solution was cooled, the solvent was concentrated under reduced pressure, and the residue was dissolved in 10 mL of dichloromethane. The solution was added dropwise to a solution obtained by mixing 4.14 g (31.1 mmol) of aluminum chloride and 30 mL of dichloromethane and cooling to 5°C. 4.22 g (25.9 mmol) of N,N-diethyl-m-toluidine was further added dropwise to the solution, and the mixture was stirred at room temperature (23°C to 28°C) for 1 hour after the addition. After the solution was poured into water, a 48% aqueous sodium hydroxide solution was added to adjust the pH to 10. After diluting with 50 mL of water, 50 mL of dichloromethane was added, and the organic layer was extracted. The organic layer was concentrated under reduced pressure and the residue was purified by column chromatography (carrier: silica gel, solvent: heptane / ethyl acetate = 90 / 10 (volume ratio)). The solvent was distilled off under reduced pressure to obtain the following (Intermediate 200) (2.50 g, yield 29%).

[0264]

Chemical formula 41

[0265]

[0266] Next, 2.50 g (7.39 mmol) of N-ethyl-1-naphthylamine, 1.26 g (7.39 mmol) of the above (Intermediate 200), 25 mL of toluene, and 3.40 g (22.2 mmol) of phosphorus oxychloride were added to the reaction container. The solution was stirred at 100°C for 5 hours and then cooled to room temperature (23°C to 28°C). 24 mL of 1M aqueous hydrochloric acid solution and 50 mL of dichloromethane were added to the solution to extract the organic layer. After the organic layer was concentrated under reduced pressure, the residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane / methanol = 100 / 0 to 90 / 10 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 80°C to obtain the following (Intermediate 201) (2.50 g, yield 64.1%).

[0267]

Chemical formula 42

[0268]

[0269] Next, in the synthesis of compound (C-2) of Synthesis Example 2, except that (Intermediate 104) was changed to the above-mentioned (Intermediate 201), a purple solid (2.70 g, yield 92%) of comparative example compound (D-3) represented by the following formula was obtained by the same method.

[0270] The obtained purple solid was subjected to NMR measurement, and the following 42 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (D-3).

[0271] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 8.07 (1H), 7.51 (2H), 7.32 (4H), 7.09 (1H), 6.74 (3H), 6.59 (3H), 3.65-3.48 (10H), 1.75 (3H), 1.49 (3H), 1.30 (12H).

[0272]

Chemical formula 43

[0273]

[0274] [Synthesis of Comparative Example Compound (D-4)]

[0275] Add 44.4 g (367 mmol) of N-ethylaniline and 140 mL of DMF to the reaction container, and cool to 5°C while stirring. Add 41.1 g (367 mmol) of potassium tert-butoxide to the solution in four portions. Further, add dropwise a solution obtained by dissolving 20.0 g (91.7 mmol) of 4,4'-difluorobenzophenone in 80 mL of DMF. After the addition, warm to room temperature and stir for 18 hours. Add 400 mL of water, 400 mL of ethyl acetate, and 100 mL of heptane to the reaction solution to extract the organic layer. Wash the organic layer twice with 300 mL of water. Add anhydrous magnesium sulfate to the organic layer, dry it, and filter it. Concentrate the filtrate under reduced pressure, dissolve the residue in 300 mL of dichloromethane and 15 mL of ethyl acetate, add 60 g of silica gel, and stir at room temperature for 30 minutes. Filter the solution, concentrate the filtrate under reduced pressure, add heptane, and crystallize. The solid was collected by filtration and dried under reduced pressure at 60°C to obtain the following (Intermediate 202) (27.4 g, yield 71%).

[0276]

Chemical formula 44

[0277]

[0278] Next, the following (Intermediate 203) (2.50 g, yield 34%) was obtained by the same method except that (Intermediate 200) was changed to the above-mentioned (Intermediate 202) in the synthesis of (Intermediate 201) of Comparative Example Compound (D-3).

[0279]

Chemical formula 45

[0280]

[0281] In the synthesis of compound (C-2) of Synthesis Example 2, except that (Intermediate 104) was replaced by the above-mentioned (Intermediate 203), the target compound (D-4) was obtained as a purple solid (1.92 g, yield 91%) by the same method.

[0282] The obtained purple solid was subjected to NMR measurement, and the following 40 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (D-4).

[0283] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 8.14 (1H), 7.56-7.22 (19H), 6.71 (5H), 3.93 (4H), 3.63 (2H), 1.48 (3H), 1.35 (6H).

[0284]

Chemical formula 46

[0285]

[0286] [Synthesis of Comparative Example Compound (D-5)]

[0287] 20.0 g (150 mmol) of 1,2,3,4-tetrahydroquinoline, 33.7 g (180 mmol) of 1-iodobutane, 41.5 g (300 mmol) of potassium carbonate, and 100 mL of DMF were added to a reaction container, and the mixture was stirred at 80°C for 15 hours. After the reaction solution was cooled, 200 mL of ethyl acetate was added, and the mixture was stirred at room temperature (23°C to 28°C), and then filtered. 100 mL of heptane and 300 mL of water were added to the filtrate, and the organic layer was extracted. After further washing with 300 mL of water twice, the organic layer was extracted. Anhydrous magnesium sulfate was added, the organic layer was dried, filtered, and the filtrate was concentrated under reduced pressure. After the residue was dissolved in 300 mL of heptane, 30 g of silica gel was added, and the mixture was stirred at room temperature (23°C to 28°C) for 30 minutes, and then filtered. The filtrate was concentrated under reduced pressure to obtain the following (Intermediate 204) (23.9 g, yield 84%).

[0288]

Chemical formula 47

[0289]

[0290] Next, 3.00 g (16.9 mmol) of 4-diethylaminobenzaldehyde, 6.50 g (34.4 mmol) of the above (intermediate 204), 0.51 g (8.46 mmol) of urea, 2.8 mL (33.9 mmol) of concentrated hydrochloric acid, and 45 mL of ethyl cellosolve were added to the reaction vessel, and the mixture was stirred at 90° C. for 4 hours. The reaction solution was poured into 250 mL of water, and 3.50 g of sodium carbonate was added, and the mixture was stirred at room temperature (23° C. to 28° C.). After removing the supernatant, the residue was dissolved in dichloromethane, and dried by adding magnesium sulfate. The solution was filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane / heptane = 60 / 40 to 100 / 0 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 60°C to obtain the following (Intermediate 205) (5.12 g, yield 56%).

[0291]

Chemical formula 48

[0292]

[0293] Next, 5.10 g (9.48 mmol) of the (intermediate 205) and 51 mL of dichloromethane were added to the reaction container, stirred, and after the solid was dissolved, 3.50 g (14.2 mmol) of tetrachlorobenzoquinone was added. After stirring at room temperature (23°C to 28°C) for 1 hour, 1.0 mL of concentrated hydrochloric acid was added and further stirred for 30 minutes. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane / methanol = 100 / 1 to 10 / 1 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was suspended and washed with heptane, and after filtering the solid, it was dried under reduced pressure at 80°C to obtain the following (intermediate 206) (4.53 g, yield 83%).

[0294]

Chemical formula 49

[0295]

[0296] Next, 3.50 g (6.12 mmol) of the (intermediate 206), 42 mL of water, and 21 mL of methanol were added to the reaction vessel, stirred at 60°C, and after the solid was dissolved, 1.76 g (6.12 mmol) of LiN(SO2CF3)2 was added. After stirring at 60°C for 1 hour, the mixture was cooled and the precipitated solid was filtered out. 50 mL of water was added to the obtained solid, and after suspension washing at 50°C, the solid was filtered out. The obtained solid was dried under reduced pressure at 80°C to obtain a blue solid (4.63 g, yield 93%) of the comparative example compound (D-5) represented by the following formula.

[0297] The obtained blue solid was subjected to NMR measurement, and the following 50 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (D-5).

[0298] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 7.29 (2H), 7.18 (2H), 7.04 (2H), 6.78 (2H), 6.70 (2H), 3.56(8H), 3.47(4H), 2.77(4H), 2.02(4H), 1.69(4H), 1.44(4H), 1.32(6H), 1.00(6H).

[0299]

Chemical formula 50

[0300]

[0301] [Synthesis of Comparative Example Compound (D-6)]

[0302] In the synthesis of (Intermediate 201) of the comparative example compound (D-3), except that N-ethyl-1-naphthylamine was changed to (Intermediate 204) and the (Intermediate 200) was changed to 4,4'-bis(diethylamino)benzophenone, the following (Intermediate 207) (5.15 g, yield 53%) was obtained by the same method.

[0303]

Chemical formula 51

[0304]

[0305] Next, in the synthesis of compound (C-2) of Synthesis Example 2, except that (Intermediate 104) was changed to the above-mentioned (Intermediate 207), a dark green solid (4.91 g, yield 75%) of comparative example compound (D-6) represented by the following formula was obtained by the same method.

[0306] The obtained dark green solid was subjected to NMR measurement, and the following 46 hydrogen signals were detected, and the structure was identified as a compound represented by the following formula (D-6).

[0307] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.25 (4H), 7.15 (1H), 7.05 (1H), 6.95 (5H), 3. 59-3.50(12H), 2.73(2H), 1.90(2H), 1.62(2H), 1.38(2H), 1.20(12H), 0.95(3H).

[0308]

Chemical formula 52

[0309]

[0310] [Example 1]

[0311] (Determination of maximum absorption wavelength)

[0312] The compound (C-1) obtained in Synthesis Example 1 was dissolved in propylene glycol monomethyl ether (PGME) to prepare a solution with a concentration of 0.01 mmol / L. The ultraviolet-visible absorption spectrum (wavelength range of 350 to 800 nm) was measured at room temperature (25° C.) as a spectral characteristic using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, model: V-650), and the maximum absorption wavelength in the measured wavelength range was measured. The measurement results are shown in Table 1.

[0313] (Determination of 5% mass loss temperature)

[0314] The compound (C-1) obtained in Synthesis Example 1 was subjected to TG-DTA measurement (sample mass: 5.0 mg to 6.0 mg, heating rate: 10°C / min) under nitrogen flow using a thermogravimetric differential thermal analyzer (MAC Science Co., Ltd., model: TG-DTA 2000S) to measure the 5% mass loss temperature. The measurement results are shown in Table 1.

[0315] (Evaluation of heat resistance)

[0316] Add 20 mg of the compound (C-1) obtained in Synthesis Example 1 and 5 g of a 25% by mass DMF-PGMEA mixed solution of a copolymer of methacrylic acid, acrylate and styrene to a sample bottle, and stir for 30 minutes to mix. The obtained colored resin solution was filtered with a syringe filter, and 1 g of the filtrate was applied to a glass substrate (spin coating method, 1000 rpm-6 seconds), and heated and dried at 100°C for 2 minutes to form a thin film. The color value of the obtained film was measured using a spectrophotometer (manufactured by Konica Minolta Co., Ltd., model: CM-5). Thereafter, the film was heated at 230°C for 20 minutes, and the color value was measured in the same manner. The color difference (ΔE ＊ ab ) was used as an indicator of heat resistance, and the results are shown in Table 1.

[0317] [Example 2 to Example 10]

[0318] The maximum absorption wavelength, 5% mass loss temperature and heat resistance were measured in the same manner as in Example 1, except that the compounds (C-2) to (C-10) obtained in Synthesis Examples 2 to 10 were used instead of the compound (C-1) in Example 1. The results are summarized in Table 1.

[0319] [Comparative Example 1 to Comparative Example 6]

[0320] For comparison, the maximum absorption wavelength, the 5% mass reduction temperature, and the heat resistance were measured in the same manner as in Example 1, except that the comparative example compounds (D-1) to (D-6) not belonging to the present invention were used instead of the example compound (C-1). The results are summarized in Table 1.

[0321]

Table 1

[0322]

[0323]

[0324] As shown in Table 1, the triarylmethane dyes of the compounds of the examples of the present invention are superior to the triarylmethane dyes of the comparative examples in that the 5% mass loss temperature and the heat resistance during film formation are higher. From the comparison with Comparative Examples 1 to 5, it can be understood that the high heat resistance is obtained by having a tetrahydroquinoline skeleton, and from the comparison with Comparative Example 6, it can be understood that the high heat resistance is obtained by having a substituent in the tetrahydroquinoline skeleton.

[0325] The coloring composition containing the triarylmethane pigment of the present invention has high heat resistance and can be used as a pigment material for various purposes such as a colorant for color filters. In addition, by using the coloring composition as a colorant for color filters, a color filter with excellent color characteristics (color gamut, brightness, contrast, etc.) can be produced.

Claims

1. A triarylmethane pigment represented by the following general formula (1): 【Chemical formula 1】 In formula (1), R 1 ~R 5 Respectively represent ―H, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent, R 1 With R 2 , R 3 With R 4 can bond to each other to form a ring, R 6 ~R 10 Each independently represents -H, a halogen atom, -OH, -CF3, -NO2, -CN, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms which may have a substituent, R 11 ~R 14 Respectively represent ―H, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, R 8 and R 12 ~R 14 At least one of them represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, An represents an anion, and m represents a natural number.

2. The triarylmethane dye according to claim 1, wherein In the general formula (1), R 1 and R 3 Each independently is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

3. The triarylmethane dye according to claim 2, wherein In the general formula (1), R 1 and R 3 same.

4. The triarylmethane dye according to claim 1, wherein In the general formula (1), R 5 It is a linear alkyl group having 1 to 3 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

5. The triarylmethane dye according to claim 1, wherein In the general formula (1), R 11 For -H, R 8 , R 12 ~R 14 It is a linear alkyl group having 1 to 3 carbon atoms which may have a substituent.

6. The triarylmethane dye according to claim 1, wherein In the general formula (1), An is a perfluoroalkylsulfonic acid anion, a perfluoroalkylsulfonyl imide anion, a tris(trifluoromethanesulfonyl)methide anion or a heteropolyacid anion.

7. The triarylmethane dye according to claim 1, wherein The triarylmethane dye of the general formula (1) has an absorption band with a maximum absorption wavelength of 570 nm to 640 nm in an ultraviolet-visible absorption spectrum (wavelength range of 350 to 800 nm) measured at 23 to 27° C. using a propylene glycol monomethyl ether (PGME) solution.

8. The triarylmethane dye according to claim 1, wherein The 5% mass loss temperature of the triarylmethane dye of the general formula (1) measured by TG-DTA (sample mass: 5.0 mg to 6.0 mg, heating rate: 10°C / min) using a thermogravimetric-differential thermal analyzer under a nitrogen flow (nitrogen flow rate: 50 mL / min) is 270°C or higher. 9 . A coloring composition comprising the triarylmethane dye according to claim 1 . 10 . A colorant for color filter, comprising the coloring composition according to claim 9 . 11 . A color filter using the colorant for color filter according to claim 10 .

Images